KR100357352B1 - Oil-in-water emulsions and pesticide compositions containing them - Google Patents

Abstract

PCT No. PCT/EP94/04142 Sec. 371 Date Sep. 5, 1996 Sec. 102(e) Date Sep. 5, 1996 PCT Filed Dec. 14, 1994 PCT Pub. No. WO95/17088 PCT Pub. Date Jun. 29, 1995The present invention relates to oil-in-water emulsions containing 0.001 to 70% by weight of at least one active substance from the group consisting of phosphates, thiophosphates and/or carbamates, 0.001 to 30% by weight of one or more surfactant compounds from the group consisting of ethoxylated fatty amines or of phosphorylated fatty amine ethoxylates, and also, if desired, adjuvants and water to make up 100% by weight.

Description

Oil-in-water emulsions containing phosphorylated surfactants are known in the prior art.

EP-A 0 224 846 describes aqueous emulsion based plant protection agents containing the active ingredient and alpha- and omega-phosphorylated ethylene oxide / propylene oxide / ethylene oxide block copolymers or salts thereof as dispersants. A disadvantage of these emulsions is that they are substantially free of water immiscible organic solvents.

EP-A 0 118 759 discloses salts of propylene oxide and ethylene oxide based phosphorylated block copolymers of the general formula Plant protection agents in the form of aqueous emulsion concentrates containing from 20% by weight are described.

Where

r and s are independently of each other a number from 20 to 300,

t is a number from 10 to 300,

n and m are each independently 1 or 2 and n + m must be 3,

M is an alkali metal cation, one equivalent of alkaline earth metal cation, ammonium, alkylammonium or alkanolammonium.

Mentioned as suitable active ingredients are only hydrolysable insecticides, herbicides and pheromones.

US-A 4,107,302 relates to an aqueous pesticide concentrate mixture containing an active ingredient and a surfactant compound of the group consisting of phosphates and / or thiophosphates. As nonionic surfactant compounds, preference is given to using ethoxylated alkylallylphenyl ethers, for example distyrylmethylphenol ethoxylates having 10 EO. A disadvantage of the mixtures described herein is the need to adjust the pH range to 3.0 to 8.5 using aqueous buffer. In addition, organic solvents such as ketones, ethers and alcohols are added for mixtures with an active ingredient content greater than 30% by weight.

EP-A 0 196 469 discloses a surfactant used to disperse the active ingredient, an aqueous solution of an ethylene oxide / propylene oxide / ethylene oxide block copolymer having an average molecular weight of 2000 to 8000 and an HLB value of 8 to 30; and / Or a phosphate-containing macroemulsion which is an aqueous solution of nonylphenol-propylene oxide-ethylene oxide adduct. The macroemulsions described must contain glycerol as an adjuvant. When using an active ingredient which is solid at room temperature, a solution of that ingredient in an aromatic diluent is used.

EP-A 0 130 370 relates to a plant protection agent combination obtained by mixing an active ingredient dispersion with an active ingredient solution. The plant protection agent formulations prepared in this way are phosphorylated surfactants, for example the Na salts of C ₁₂ -C ₁₈ alkyl polyglycol ether phosphate mono / diesters [ ^? Forlanit P, Henkel KGaA] and triethanolamide salts of a mixture of mono- and difosylates of tristyrylphenol polyglycol ether of 18 EO units [ ^? Soprophor FI, Rhone-Poulenc] and sulfated and sulfonated surfactant compounds, for example, contain Na salts and Na lignin sulfonates of sulfosuccinic acid monoesters. A disadvantage of the plant protection agent formulations described herein is the use of active ingredient solutions containing high concentrations (40 to 48% by weight) of organic solvents such as xylene and methyl naphthalene.

Similarly, oil-in-water emulsions containing nonionic surfactants as dispersants are known in the art.

EP-A 0 289 909 discloses, in addition to the active ingredients, organic, nonionic block copolymers, copolymers or coblock copolymers as surfactants, and essentially containing urea to provide adequate phase stability. It relates to a stable aqueous emulsion of phosphorus pesticides.

It is an object of the present invention in the form of an aqueous emulsion concentrate based on an active ingredient selected from the group consisting of phosphate thiophosphate and / or carbamate, in particular an active ingredient sensitive to hydrolysis, containing no organic solvent and without chemical stability and physical stability. This is to provide a plant protection formulation which is excellent, particularly resistant to hydrolysis, stable even at low temperatures (-10 ° C.) and, if necessary, can be diluted with water, alone or in admixture with other liquid formulations.

It has been found by the present invention that surprisingly, preferred plant protection compositions can be obtained by using certain surfactant compounds. In particular, these surfactant compounds are fatty amine ethoxylates (A) of formula (I) and phosphorylated fatty amine ethoxylates (B) of formula (II).

The present invention comprises 0.001 to 70% by weight, preferably 0.5 to 50% by weight, of at least one active ingredient selected from the group consisting of phosphate, thiophosphate and / or carbamate,

0.001 to 30% by weight, preferably at least one surfactant selected from the group consisting of ethoxylated fatty amines (A) of formula (I) and phosphorylated fatty amine ethoxylates (B) of formula (II) Is 0.1 to 20% by weight,

If necessary, it relates to an oil-in-water emulsion comprising an adjuvant and an amount of water up to 100% by weight.

Where

R ¹ is hydrogen, C ₁ -C ₂₄ alkyl, C ₂ -C ₂₄ alkenyl, C ₂ -C ₂₄ alkynyl, C ₅ -C ₂₄ cycloalkyl, C ₆ -C ₃₆ aryl, C ₆ -C ₄₈ alk a Aryl, C ₆ -C ₃₆ heteroaryl, or C ₆ -C ₄₈ heteroalkaryl,

R ² is R ^1, or the general formula, except for hydrogen _{(CH 2 -CH 2 -O) y} -H,

x and y are independently a number from 1 to 200.

Where

R ¹ is hydrogen, C ₁ -C ₂₄ alkyl, C ₂ -C ₂₄ alkenyl, C ₂ -C ₂₄ alkynyl, C ₅ -C ₂₄ cycloalkyl, C ₆ -C ₃₆ aryl, C ₆ -C ₄₈ alk a Aryl, C ₆ -C ₃₆ heteroaryl, or C ₆ -C ₄₈ heteroalkaryl,

R ² is R ¹ except hydrogen or a general formula Is a group of

R ³ and R ⁴ independently of one another are hydrogen, alkali metal cations, 1 equivalent of alkaline earth metal ions, ammonium, mono-, di- or tri (C ₁ -C ₁₂ alkyl) ammonium or mono-, di- or tri (C _1- C ₁₂ alkanol) ammonium

x and y are independently a number from 1 to 200.

The O / W emulsions according to the present invention can be prepared from one or more agrochemically active ingredients, active ingredients for controlling harmful organisms in the field of household and sanitation and / or pharmacologically active ingredients selected from the phosphate, thiophosphate and / or carbamate classes. It contains. In this regard, suitable active ingredients, preferably those sensitive to hydrolysis, include both components which are liquid at room temperature and those which are solid at room temperature. Such active ingredients are known and described, for example, in "The Pesticide Manual" 9th edition, The British Crop. Protection Council, 1991].

As used herein, the term agrochemical component means a component conventionally used for plant protection. Examples of these include insecticides, acaricides, fungicides, nematicides, herbicides, molluscs exterminators, insecticides, growth regulators, toxic modifiers, adjuvants, fertilizers and acaricides.

Specific examples of such active ingredients are 0,0-diethyl 0- [2-isopropyl-4-methyl-6-pyrimidyl] thiophosphate (diazinone), 0,0-diethyl 0- [3,5, 6-trichloro-2-pyridyl] thiophosphate (chloropyrophosph), 2- (1-methylpropyl) phenyl methyl carbamate (BPMC), 0,0-dimethyl S-methylcarbamoylmethylthiophosphate (dimetho ), Chlorobicyclo [3.2.0] hepta-2,6-dien-6-yl phosphate (heptenophosph), 0,0-diethyl 0-1-phenyl-1H-1,2,4-tria Zol-3-yl Thiophosphate (Triazophosph), Ethyl 2-diethoxyphosphinothioyloxy-5-methylpyrazolyl [1,5-α] pyrimidine-6-carboxylate (pyrazophos), 0 , 0-diethyl 0- (4-nitrophenyl) thionophosphate, 0,0-dimethyl 0- (4-nitrophenyl) thionophosphate (phenythithion), 0-ethyl 0-4-methylthiophenyl S -Propyl dithiophosphate, 2-isopropoxyphenyl N-methylcarbamate, 2,3-dihydro-2,2-dimethyl-7-benzofu Methylcarbamate, 3,5-dimethyl-4-methyl thiophenyl N-methylcarbamate, 0,0-diethyl 0- (3-chloro-4-methyl-7-coumarinyl) thiophosphate, S- [1 , 2-bis (ethoxycarbonyl) ethyl] 0,0-dimethyl dithiophosphate (malation), 0,0-dimethyl 0-4-methylmercapto-3-methylphenyl thionophosphate (pention, leviside) ) And 0-ethyl 0-2-isopropyloxycarbonylphenyl-N-isopropylthionophosphoramide.

In the present invention, the active ingredient for controlling pests in the home and sanitation field is all conventional active ingredients having low solubility in water. Examples of such active ingredients are 2-isopropoxyphenyl N-methylcarbamate, 0,0-diethyl 0-4-nitrophenyl thionophosphate (ethyl-parathion), 0,0-dimethyl 0-4-nitrophenyl Thiophosphate (methyl-parathion), S- [1,2-bis (ethoxycarbonyl) ethyl] 0, 0-dimethyl dithiophosphate, 0,0-dimethyl 0-3-methyl-4-nitrophenyl thi Onophosphate (sumithion, polythione) and 0,0-dimethyl 0-4-methylmercapto-3-methylphenyl thionophosphate (Leviside, pention).

In the present invention, the pharmacologically active component is a component having low solubility in water, which can be preferably used in the veterinary field. An example of such an active ingredient is chlorobicyclo [3.2.0] hepta-2,6-diene-6-ylphosphate (heptenoforce).

The composition according to the invention contains at least one compound of general formula (I) or (II).

In the compounds of formula (I), R ¹ is preferably hydrogen, C ₁₀ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, C ₆ -C ₂₀ cycloalkyl, C ₆ -C ₁₈ aryl or (C ₁ -C ₁₂ alkyl) ₃ -phenyl, in particular C ₁ -C ₁₂ alkylphenyl or mono-, di- or tristyrylphenyl.

R ² is preferably C ₁₀ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, C ₆ -C ₂₀ cycloalkyl, C ₆ -C ₁₈ aryl, (C ₁ -C ₁₂ alkyl) ₃ -phenyl, in particular C _1- C ₁₂ alkylphenyl, mono-, di- or tristyrylphenyl or a group of the general formula (CH ₂ -CH ₂ -O) _y -H, wherein y is a number from 1 to 120.

Since the amines used for the synthesis of compounds of general formula (I), in particular fatty amines in which R ¹ and / or R ² are alkyl and / or alkenyl groups, are generally random mixtures of homologues and isomers, these radicals R ¹ and It is advantageous to mention the average carbon number for R ² .

The radicals R ¹ and R ² may have suitable substituents such as halogen atoms, alkoxy groups, hydroxyl groups, nitro groups, amino groups and / or carboxyl ester groups when they are not hydrogen.

x and y are the moles of ethylene oxide units. The preferred range of x and y is 1 to 120, preferably 1 to 80, in particular 1 to 30.

Very particularly suitable fatty amine ethoxylates of formula (I) are coconut fatty amine ethoxylates, oleylamine ethoxylates, stearylamine ethoxylates and tallow fatty amine ethoxylates, where x is from 1 to 40 Is the number of and corresponding bisethoxylates thereof, where x and y are independently of each other a number from 1 to 40.

The surfactant of general formula (I) can be manufactured by a simple method. Typically these compounds are prepared by ethoxylating the amines on which they are based (K. Kosswig and H. Stache, "Die Tenside" [The Surfactants], Hauser-Verlag, p. 157).

In the case of compounds of formula (II), R ¹ is preferably C ₁₀ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, C ₆ -C ₂₀ aryl, C ₁ -C ₁₂ alkylphenyl or mono-, di Or tristyrylphenyl.

R ² is preferably C ₁₀ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, C ₆ -C ₂₀ aryl, C ₁ -C ₁₂ alkylphenyl or mono-, di- or tristyrylphenyl or a general formula

Group of y, R ³ and R ⁴ are described below.

Since the amines used for the synthesis of compounds of general formula (II), in particular fatty amines in which R ¹ and / or R ² are alkyl and / or alkenyl groups, are generally random mixtures of homologues and isomers, these radicals R ¹ and It is advantageous to mention the average carbon number for R ² .

If the radicals R ¹ and R ² are not hydrogen, they may have suitable substituents, for example halogen atoms, alkoxy groups, hydroxyl groups, nitro groups, amino groups and / or carboxyl ester groups.

Preferred ranges for x and y are 1 to 120, preferably 1 to 80, in particular 1 to 30. R ³ and R ⁴ independently of one another are preferably hydrogen, alkali metal ions, mono-, di- or tri (C ₂ -C ₄ alkyl) ammonium or tri (C ₂ -C ₄ alkanol) ammonium.

Surfactants of the general formula (II) can be prepared by a simple method. Typically these compounds are prepared by reacting the amine ethoxylates on which they are based with polyphosphoric acid or phosphorus pentoxide (K. Kosswig, loc. Cit., P. 133).

The O / W emulsions according to the invention contain water as a continuous phase. In the case of concentrated emulsions, the proportion of water is relatively low, while the diluted emulsion contains relatively large amounts of water. The oil phase (dispersed phase) is in the form of finely divided droplets in the aqueous phase, and the finely divided droplet sizes can vary within a certain range. The particle diameter of the droplets is generally from 0.001 to 10 μm, preferably from 0.01 to 5 μm.

These O / W emulsions advantageously contain no organic solvents. Thus, they have a high flash point, low flammability and are actually odorless.

Adjuvants which may be present in oil-in-water emulsions according to the invention are preservatives, low temperature stabilizers, dyes and fragrance improvers. Examples of preservatives are 2-hydroxybiphenyl, sorbic acid, p-hydroxybenzaldehyde, methyl p-hydroxybenzoate, benzaldehyde, benzoic acid, propyl p-hydroxybenzoate and p-nitrophenol. The amount of preservative in the emulsion may be 0.01 to 1% by weight. Suitable low temperature stabilizers are glycols, glycerol, polyethylene glycols, sugars, and salts such as hammonium sulfate and sodium oleate, and typically the concentration of the emulsion may be from 1 to 10% by weight. Examples of dyes are azo dyes and phthalocyanine dyes. Aroma enhancers that can be used are perfume oils.

One example of a suitable method for preparing these O / W emulsions is described in the literature (see EP-B 0 130 370). In principle, however, the two phases can be formed in the desired state by stirring.

Oil-in-water emulsions are characterized by being stable under practical general conditions. During long-term storage, these emulsions are characterized by physical stability and the content of active ingredients at high temperatures (50 ° C) and low temperatures (-5 ° C, -10 ° C). There is no change. A further advantage is that active ingredients that are solid or liquid at room temperature are emulsified at equal success rates. It is not necessary to add glycerol and organic solvents, especially when solid active ingredients are used (see EP-A 0 196 463).

Oil-in-water emulsions according to the invention can be used either as prepared or after dilution in advance. In this regard, their use depends on the concentration of the oil-in-water emulsion and the specific instructions. The emulsion is used in a conventional manner, for example sprayed or poured. Oil-in-water emulsions according to the invention have been found to have excellent activity against harmful organisms such as aphids, cereal weevils, cherry beetles and soy weevil. In this regard, no plant toxicity should be detected for plants, in particular for dwarf kidney beans, wild legumes, tomatoes, cucumbers, wild apple stems and vines.

Example

Plant protection composition having a surfactant of formula (I):

Table I contains bisethoxylated tallow fatty amines [R ¹ = C ₁₄ (5%), C ₁₆ (30%), C ₁₈ (65%), x = 7, y = 8] as surfactant compounds, An oil-in-water emulsion according to the invention is shown.

The emulsion is stable during storage for at least 1 month (storage temperature: 25 ° C, 50 ° C).

TABLE I

Plant protection composition having a surfactant of formula (II):

Table II shows that R ¹ is C ₁₄ (5%), C ₁₆ (30%), C ₁₈ (65%), and R ² is a general formula

Represents an oil-in-water emulsion according to the invention containing phosphorylated fatty amine bisethoxylates of the general formula (II), wherein the groups of (R ³ and R ⁴ are hydrogen, x is 7 and y is 8). .

TABLE II

Claims (11)

0.001 to 70% by weight of one or more active ingredients selected from the group consisting of phosphate, thiophosphate and carbamate, 0.001 to 30% by weight of at least one surfactant compound selected from the group consisting of ethoxylated fatty amines (A) of formula (I) and phosphorylated fatty amine ethoxylates (B), If necessary, an oil-in-water emulsion comprising an adjuvant and an amount of water up to 100% by weight, provided that the surfactant compound in the oil-in-water emulsion comprises at least one surfactant of the general formula (I), And no combinations with lysylated styrene substituted phenols or salts thereof. Where R ¹ is hydrogen, C ₁ -C ₂₄ alkyl, C ₂ -C ₂₄ alkenyl, C ₂ -C ₂₄ alkynyl, C ₅ -C ₂₄ cycloalkyl, C ₆ -C ₃₆ aryl, C ₆ -C ₄₈ alk a Aryl, C ₆ -C ₃₆ heteroaryl, or C ₆ -C ₄₈ heteroalkaryl, R ² is a group of R ¹ or general formula (CH ₂ -CH ₂ -O) _y -H excluding hydrogen, x and y are independently a number from 1 to 200. Where R ¹ is hydrogen, C ₁ -C ₂₄ alkyl, C ₂ -C ₂₄ alkenyl, C ₂ -C ₂₄ alkynyl, C ₅ -C ₂₄ cycloalkyl, C ₆ -C ₃₆ aryl, C ₆ -C ₄₈ alk a Aryl, C ₆ -C ₃₆ heteroaryl, or C ₆ -C ₄₈ heteroalkaryl, R ² is R ¹ except hydrogen or a general formula Is a group of R ³ and R ⁴ independently of one another are hydrogen, alkali metal cations, 1 equivalent of alkaline earth metal ions, ammonium, mono-, di- or tri (C ₁ -C ₁₂ alkyl) ammonium or mono-, di- or tri (C ₁ -C ₁₂ alkanol) ammonium, x and y are independently a number from 1 to 200. A surfactant compound according to claim 1, wherein in the surfactant compound which is an ethoxylated fatty amine of formula (I), R ¹ is hydrogen, C ₁₀ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, C ₆ -C ₂₀ cycloalkyl, An oil-in-water emulsion that is C ₆ -C ₁₈ aryl, (C ₁ -C ₁₂ alkyl) ₃ phenyl or mono-, di- or tristyrylphenyl. 3. The compound of claim 1, wherein R ² is C ₁ -C ₁₀ alkyl, C ₂ -C ₁₈ alkenyl, C ₆ -C ₂₀ cycloalkyl, C ₆ -C ₁₈ aryl, (C ₁ -C ₁₂ alkyl ) Oil-in-water emulsion which is a ₃ -phenyl, mono-, di- or tristyrylphenyl or group of the general formula (CH ₂ -CH ₂ -O) _y -H, wherein y is a number from 1 to 120. The oil-in-water emulsion according to claim 1 or 2, wherein in the surfactant compound which is an ethoxylated fatty amine of general formula (I), x and y are independently of each other water of 1 to 120. A surfactant compound according to claim 1, wherein in the surfactant compound which is a phosphorylated fatty amine ethoxylate of formula (II), R ¹ is C ₁₀ -C ₁₈ alkyl, C ₂ -C ₁₀ alkenyl, C ₆ -C ₂₀ aryl Oil-in-water emulsion, which is C ₁ -C ₁₂ alkylphenyl or mono-, di- or tristyrylphenyl. A surfactant compound according to claim 1 or 5, wherein in the surfactant compound which is phosphorylated fatty amine ethoxylate of formula (II), R ² is C ₁₀ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, C ₆ -C ₂₀ aryl, C ₁ -C ₁₂ alkylphenyl, mono-, di- or tristyrylphenyl or a general formula Wherein R ³ and R ⁴ are independently of each other hydrogen, alkali metal ions, mono-, di- or tri (C ₂ -C ₄ alkyl) ammonium or tri (C ₂ -C ₄ alkanol) ammonium, y is a number from 1 to 120]. The oil-in-water emulsion according to claim 1 or 5, wherein x and y are independently of each other water of 1 to 120. The oil-in-water emulsion according to claim 1 or 2, comprising as an adjuvant one or more selected from the group consisting of preservatives, low temperature stabilizers, dyes and flavor improvers. The oil-in-water emulsion according to claim 1 or 2, wherein the oil phase is in the form of finely divided droplets. The oil-in-water emulsion according to claim 1 or 2, wherein the finely divided droplets have a particle diameter of 0.001 to 10 µm. A pesticide composition containing an oil-in-water emulsion according to claim 1.